JP6740801B2 - High-purity copper electrolytic refining additive and high-purity copper manufacturing method - Google Patents
High-purity copper electrolytic refining additive and high-purity copper manufacturing method Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 139
- 229910052802 copper Inorganic materials 0.000 title claims description 138
- 239000010949 copper Substances 0.000 title claims description 138
- 239000000654 additive Substances 0.000 title claims description 47
- 230000000996 additive effect Effects 0.000 title claims description 46
- 238000007670 refining Methods 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- -1 polyoxyethylene monophenyl ether Polymers 0.000 claims description 46
- 229910052709 silver Inorganic materials 0.000 claims description 44
- 239000004332 silver Substances 0.000 claims description 44
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 41
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 41
- 239000008151 electrolyte solution Substances 0.000 claims description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 36
- 239000012535 impurity Substances 0.000 claims description 36
- 150000003536 tetrazoles Chemical class 0.000 claims description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 25
- 239000000460 chlorine Substances 0.000 claims description 25
- 229910052801 chlorine Inorganic materials 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 239000002736 nonionic surfactant Substances 0.000 claims description 12
- 125000001165 hydrophobic group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 238000007127 saponification reaction Methods 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 230000002040 relaxant effect Effects 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 description 68
- ZYDVNTYVDVZMKF-UHFFFAOYSA-N [Cl].[Ag] Chemical compound [Cl].[Ag] ZYDVNTYVDVZMKF-UHFFFAOYSA-N 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 229910052717 sulfur Inorganic materials 0.000 description 16
- 239000011593 sulfur Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 10
- 210000001787 dendrite Anatomy 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 7
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Electrolytic Production Of Metals (AREA)
Description
本発明は、塩素および銀の少ない高純度の銅を製造する銅電解精錬用の添加剤とその高純度銅製造方法に関する。 The present invention relates to an additive for copper electrolytic refining for producing high-purity copper containing little chlorine and silver, and a method for producing the high-purity copper.
高純度銅の製造方法として、特許文献１に記載されているように、硫酸銅水溶液を電解し、陰極に析出した銅を陽極にしてさらに硝酸銅水溶液中において100A/m２以下の低電流密度で再電解する二段階の電解を行う方法が知られている。 As a method for producing high-purity copper, as described in Patent Document 1, a copper sulfate aqueous solution is electrolyzed, copper deposited on a cathode is used as an anode, and a low current density of 100 A/m 2 or less in a copper nitrate aqueous solution is further used. There is known a method of performing two-stage electrolysis in which re-electrolysis is carried out.
また、特許文献２に記載されているように、塩化物イオン、ニカワ等、および活性硫黄成分を含む硫酸銅電解液にＰＥＧ（ポリエチレングリコール）等のポリオキシエチレン系界面活性剤を添加することによって機械的特性とカソード密着性を高めた電解銅箔の製造方法が知られている。さらに、特許文献３に記載されているように、ＰＶＡ（ポリビニルアルコール）等の平滑化剤とＰＥＧなどのスライム促進剤を添加することによって銅表面が平滑で、不純物である銀や硫黄の含有量が少ない高純度電気銅を製造する方法が知られている。 Further, as described in Patent Document 2, by adding a polyoxyethylene-based surfactant such as PEG (polyethylene glycol) to a copper sulfate electrolytic solution containing chloride ions, glue, etc., and an active sulfur component. A method of manufacturing an electrolytic copper foil having improved mechanical properties and cathode adhesion is known. Furthermore, as described in Patent Document 3, by adding a smoothing agent such as PVA (polyvinyl alcohol) and a slime accelerator such as PEG, the copper surface is smooth and the content of impurities such as silver or sulfur is increased. There is known a method for producing high-purity electrolytic copper with less waste.
従来の銅電解精錬では、電解液に塩化物イオンが添加されており、その効果として、カソードに析出する電気銅の形態を改善すること及び、電解液中の銀イオンを塩化銀粒子として沈殿させることで、電解液中から銀イオンを析出させて、カソードへの銀の共析を防ぐことが挙げられる。しかし、塩化物イオンだけでは電解液中の銀イオンをすべて析出させることができず、さらに添加された塩化物イオンがカソードに移行し、電気銅の純度が低下するという問題があった。よって、従来の銅電解精錬では銀と塩素の含有量を低減することが難しい。 In conventional copper electrolytic refining, chloride ions are added to the electrolytic solution, and the effect is to improve the morphology of electrolytic copper deposited on the cathode and to precipitate silver ions in the electrolytic solution as silver chloride particles. Thus, silver ions can be deposited from the electrolytic solution to prevent co-deposition of silver on the cathode. However, there is a problem in that chloride ions alone cannot precipitate all the silver ions in the electrolytic solution, and the added chloride ions migrate to the cathode, resulting in a decrease in the purity of electrolytic copper. Therefore, it is difficult to reduce the contents of silver and chlorine by conventional copper electrolytic refining.
例えば、特許文献１の製造方法のように、硫酸銅浴の電解と硝酸銅浴の電解を行う二段階の製造方法では電解に手間がかかる問題がある。また、特許文献２〜３のように、ＰＥＧやＰＶＡだけではカソードに析出する電気銅の塩素および銀の含有量を十分に低減することができない。 For example, as in the manufacturing method of Patent Document 1, the two-step manufacturing method of electrolyzing a copper sulfate bath and electrolyzing a copper nitrate bath has a problem in that electrolysis takes time. Further, as in Patent Documents 2 and 3, PEG and PVA alone cannot sufficiently reduce the chlorine and silver contents of electrolytic copper deposited on the cathode.
本発明は、従来の上記問題を解決したものであり、塩素および銀の少ない高純度の銅を容易に製造する銅電解精錬用の添加剤と該添加剤を用いた高純度銅の製造方法を提供する。 The present invention is to solve the above-mentioned conventional problems, an additive for copper electrolytic refining that easily produces high-purity copper with less chlorine and silver, and a method for producing high-purity copper using the additive. provide.
本発明は、上記課題を解決する以下の高純度銅電解精錬用添加剤に関する。
〔１〕銅電解精錬の電解液に添加される添加剤であって、電気銅の銀および塩素を低減するテトラゾールまたはテトラゾール誘導体（テトラゾール類と云う）を含み、さらに電気銅の応力を緩和する平均重合度２００〜７００のポリビニルアルコールまたはその誘導体を含むことを特徴とする高純度銅電解精錬用添加剤。
〔２〕上記テトラゾール誘導体が、テトラゾールのアルキル誘導体またはアミノ誘導体またはフェニル誘導体である上記[１]に記載する高純度銅電解精錬用添加剤。
〔３〕上記ポリビニルアルコールまたはその誘導体のケン化率が７０〜９９mol％である上記[１]または上記[２]に記載する高純度銅電解精錬用添加剤。
〔４〕上記ポリビニルアルコールの誘導体が、カルボキシ変性ポリビニルアルコール、エチレン変性ポリビニルアルコール、またはポリオキシエチレン変性ポリビニルアルコールである上記[１]〜上記[３]の何れかに記載する高純度銅電解精錬用添加剤。
〔５〕上記添加剤が、上記テトラゾール類および平均重合度２００〜７００のポリビニルアルコールまたはその誘導体と共に、電気銅の不純物を低減するポリエチレングリコール、または芳香族環の疎水基とポリオキシアルキレン基の親水基とを有する非イオン性界面活性剤を含む上記[１]〜上記[４]の何れかに記載する高純度銅電解精錬用添加剤。
〔６〕上記芳香族環の疎水基とポリオキシアルキレン基の親水基とを有する非イオン性界面活性剤が、ポリオキシエチレンモノフェニルエーテル、またはポリオキシエチレンナフチルエーテルである上記[５]に記載する高純度銅電解精錬用添加剤。
The present invention relates to the following additive for high-purity copper electrolytic refining that solves the above problems.
[1] An additive that is added to an electrolytic solution of copper electrolytic refining, which contains tetrazole or a tetrazole derivative (referred to as tetrazole) that reduces silver and chlorine of electrolytic copper, and an average that relaxes the stress of electrolytic copper. An additive for high-purity electrolytic copper refining, which comprises polyvinyl alcohol having a degree of polymerization of 200 to 700 or a derivative thereof .
[2] The additive for high-purity copper electrolytic refining according to the above [1], wherein the tetrazole derivative is an alkyl derivative, an amino derivative or a phenyl derivative of tetrazole.
[3] The additive for high-purity copper electrolytic refining according to the above [1] or [2], wherein the saponification ratio of the polyvinyl alcohol or its derivative is 70 to 99 mol % .
[4] The high-purity copper electrolytic refining according to any one of [1] to [3 ] above, wherein the polyvinyl alcohol derivative is carboxy-modified polyvinyl alcohol, ethylene-modified polyvinyl alcohol, or polyoxyethylene-modified polyvinyl alcohol . Additive.
[5] The above-mentioned additive, together with the above tetrazole and polyvinyl alcohol having an average degree of polymerization of 200 to 700 or a derivative thereof, polyethylene glycol that reduces impurities of electrolytic copper, or hydrophilicity of a hydrophobic group of an aromatic ring and a polyoxyalkylene group. An additive for high-purity electrolytic copper refining according to any one of the above [1] to [4], which contains a nonionic surfactant having a base .
[6] The nonionic surfactant having a hydrophobic group of the aromatic ring and a hydrophilic group of the polyoxyalkylene group is polyoxyethylene monophenyl ether or polyoxyethylene naphthyl ether. Additive for high purity copper electrolytic refining.
本発明は、また上記高純度銅電解精錬用添加剤を用いた以下の高純度銅の製造方法に関する。
〔７〕上記[１]〜上記[６]の何れかに記載する添加剤を電解液に添加して銅電解精錬を行う高純度銅の製造方法。
〔８〕上記[７]の製造方法において、上記添加剤に含まれるテトラゾール類の添加濃度が０.１〜３０mg/Lである高純度銅の製造方法。
〔９〕上記[７]または上記[８]の製造方法において、上記添加剤に含まれる上記ポリビニルアルコールまたはその誘導体の添加濃度が０.１〜１００mg/Lである高純度銅の製造方法。
〔１０〕上記[５]または上記[６]に記載する上記添加剤を用いた上記[７]の製造方法において、上記添加剤に含まれる上記ポリエチレングリコール、または上記非イオン性界面活性剤の添加濃度が２〜５００mg/Lである高純度銅の製造方法。
〔１１〕塩素含有量５０質量ppm以下および銀含有量１質量ppm以下の高純度電気銅を製造する上記[７]〜上記[１０]の何れかに記載する製造方法。
The present invention also relates to the following method for producing high-purity copper using the above-mentioned additive for high-purity copper electrolytic refining.
[7] A method for producing high-purity copper, in which the additive according to any one of [1] to [6] above is added to an electrolytic solution to perform copper electrolytic refining .
[8] The method for producing high-purity copper according to the above-mentioned [7], wherein the addition concentration of the tetrazole contained in the additive is 0.1 to 30 mg/L.
[9] The method for producing high-purity copper according to the above-mentioned [7] or [8], wherein the addition concentration of the polyvinyl alcohol or its derivative contained in the additive is 0.1 to 100 mg/L.
[10] In the production method of the above-mentioned [7] using the above-mentioned additive described in the above-mentioned [5] or the above-mentioned [6], addition of the above-mentioned polyethylene glycol contained in the above-mentioned additive or the above-mentioned nonionic surfactant. A method for producing high-purity copper having a concentration of 2-500 mg/L.
[11] The production method according to any one of [7] to [10] above, which produces high-purity electrolytic copper having a chlorine content of 50 mass ppm or less and a silver content of 1 mass ppm or less.
〔具体的な説明〕
以下、本発明を具体的に説明する。
本発明は、銅電解精錬の電解液に添加される添加剤であって、電気銅の銀および塩素を低減するテトラゾールまたはテトラゾール誘導体（テトラゾール類と云う）を含み、さらに電気銅の応力を緩和する平均重合度２００〜７００のポリビニルアルコールまたはその誘導体を含むことを特徴とする高純度銅電解精錬用添加剤に関する。上記テトラゾール類を銀塩素低減剤と云い、上記平均重合度２００〜７００のポリビニルアルコールまたはその誘導体を応力緩和剤と云う。
また、本発明の上記添加剤は、上記テトラゾール類および上記平均重合度２００〜７００のポリビニルアルコールまたはその誘導体と共に、電気銅の不純物を低減するポリエチレングリコール、または芳香族環の疎水基とポリオキシアルキレン基の親水基とを有する非イオン性界面活性剤を含むことができる。上記ポリエチレングリコール、または芳香族環の疎水基とポリオキシアルキレン基の親水基とを有する非イオン性界面活性剤を不純物低減剤と云う。
さらに、本発明は、上記添加剤を電解液に添加して銅電解精錬を行う高純度銅の製造方法に関する。
[Specific explanation]
Hereinafter, the present invention will be specifically described.
The present invention is an additive to be added to an electrolytic solution for copper electrolytic refining, which contains tetrazole or a tetrazole derivative (referred to as tetrazole) that reduces silver and chlorine of electrolytic copper, and further relaxes the stress of electrolytic copper. The present invention relates to a high-purity copper electrolytic refining additive containing polyvinyl alcohol having an average degree of polymerization of 200 to 700 or a derivative thereof . The tetrazole is referred to as a silver chlorine reducing agent, and the polyvinyl alcohol having an average degree of polymerization of 200 to 700 or a derivative thereof is referred to as a stress relaxation agent.
In addition, the additive of the present invention, together with the tetrazole and the polyvinyl alcohol having an average degree of polymerization of 200 to 700 or a derivative thereof, polyethylene glycol that reduces impurities of electrolytic copper, or a hydrophobic group of an aromatic ring and polyoxyalkylene. A nonionic surfactant having a hydrophilic group can be included. The above-mentioned polyethylene glycol or a nonionic surfactant having a hydrophobic group of an aromatic ring and a hydrophilic group of a polyoxyalkylene group is called an impurity reducing agent.
Furthermore, the present invention relates to a method for producing high-purity copper in which the above-mentioned additive is added to an electrolytic solution to carry out copper electrolytic refining.
本発明はテトラゾール類を高純度銅電解精錬の銀塩素低減剤として用いる。テトラゾール類はテトラゾールまたはテトラゾール誘導体である。テトラゾール誘導体は、例えば、テトラゾールのアルキル誘導体、またはアミノ誘導体、またはフェニル誘導体を用いることができる。具体的には、銀塩素低減剤として、１Ｈ−テトラゾール、５−アミノ−１Ｈ−テトラゾール、５−メチル−１Ｈ−テトラゾール、５−フェニル−１Ｈ−テトラゾールなどを用いることができる。 The present invention uses tetrazoles as a silver chlorine reducing agent for high purity copper electrolytic refining. Tetrazoles are tetrazoles or tetrazole derivatives. As the tetrazole derivative, for example, an alkyl derivative of tetrazole, an amino derivative, or a phenyl derivative can be used. Specifically, 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole and the like can be used as the silver chlorine reducing agent.
本発明のテトラゾール類からなる銀塩素低減剤は、銅電解精錬において電解液に添加して使用され、電気銅の塩素および銀の含有量を低減する。銀塩素低減剤として用いるテトラゾール類は、電解液中の銀イオンと難溶性の塩を形成し、電解液中の銀イオンが減少することでカソードに銀を析出し難くし、また上記テトラゾール類は電解液中の塩化物イオンとも作用して塩化物がカソードに析出するのを防止する。一方、電解液中の銅イオンは電解液中でテトラゾール類と難溶性の塩を形成せず、銀イオンと塩化物イオンのみがテトラゾール類に選択的に作用されるので、銅イオンの電析はテトラゾール類に妨害されることなく、塩素含有量および銀含有量が大幅に少ない電気銅を得ることができる。具体的には、例えば、本発明の銀塩素低減剤を用いると、カソードに析出する電気銅の塩素濃度および銀濃度を、これを用いないときの各々約１/４〜約２/３に低減することができる。 The silver chloride reducing agent comprising tetrazole of the present invention is used by adding it to an electrolytic solution in copper electrolytic refining, and reduces the chlorine and silver contents of electrolytic copper. The tetrazole used as a silver chlorine reducing agent forms a sparingly soluble salt with silver ions in the electrolytic solution and makes it difficult to deposit silver on the cathode due to the decrease of silver ions in the electrolytic solution. It also acts on chloride ions in the electrolyte to prevent chloride from depositing on the cathode. On the other hand, the copper ion in the electrolytic solution does not form a sparingly soluble salt with the tetrazole in the electrolytic solution, and only the silver ion and the chloride ion are selectively acted on the tetrazole. It is possible to obtain electrolytic copper having a significantly low chlorine content and silver content without being disturbed by tetrazoles. Specifically, for example, when the silver chlorine reducing agent of the present invention is used, the chlorine concentration and silver concentration of electrolytic copper deposited on the cathode are reduced to about 1/4 to about 2/3 respectively when not using this. can do.
一方、従来のように塩化物イオンを電解液に添加して液中の銀イオンと反応させ、塩化銀を沈殿させる方法では、塩化物イオンだけで液中の銀イオンを全て塩化銀として沈殿させることは難しいため、カソードに銀が析出し、電気銅の銀含有量が高くなる。このため本発明のような銀含有量の少ない電気銅を得ることができない。 On the other hand, in the conventional method in which chloride ions are added to the electrolytic solution and reacted with silver ions in the solution to precipitate silver chloride, the chloride ions alone precipitate all silver ions in the solution as silver chloride. However, silver is deposited on the cathode and the silver content of electrolytic copper is high. Therefore, it is impossible to obtain electrolytic copper having a low silver content as in the present invention.
銀塩素低減剤の添加濃度（電解液中の濃度）は０.１〜３０mg/Lが好ましく、０.５〜１０mg/Lがより好ましい。銀塩素低減剤の添加濃度が０.１mg/Lよりも少ないと、十分な効果がなく、３０mg/Lより多いとカソードの電析状態が悪化し、粗大なデンドライト（以下、カソードに析出する樹枝状の析出物をデンドライトとする）が発生する。発生するデントライトは電解条件によっては、長さ２cm以上になる場合もある。 The addition concentration (concentration in the electrolytic solution) of the silver chlorine reducing agent is preferably 0.1 to 30 mg/L, more preferably 0.5 to 10 mg/L. If the added concentration of the silver chlorine reducing agent is less than 0.1 mg/L, there is no sufficient effect, and if it is more than 30 mg/L, the electrodeposition state of the cathode deteriorates, and coarse dendrites (hereinafter, the trees that deposit on the cathode are -Like precipitates are used as dendrites). The generated dendrite may have a length of 2 cm or more depending on the electrolytic conditions.
本発明の銀塩素低減剤と共に、ポリエチレングリコール、または芳香族環の疎水基とポリオキシアルキレン基の親水基とを有する非イオン性界面活性剤からなる不純物低減剤を用いることによって、電気銅の硫黄含有量を低減することができ、また銀含有量をさらに低減することができる。具体的には、例えば、ポリエチレングリコールもしくは芳香族環の疎水基とポリオキシアルキレン基の親水基とを有する非イオン性界面活性剤からなる不純物低減剤を電解液に添加することによって、電気銅の表面が平滑になり、電解液中の銀イオンおよび硫酸イオンが電気銅表面に付着し難くなるので、電気銅の銀濃度および硫黄濃度を大幅に低減することができる。 By using an impurity reducing agent comprising a nonionic surfactant having a hydrophobic group of an aromatic ring and a hydrophilic group of a polyoxyalkylene group together with the silver chlorine reducing agent of the present invention, sulfur of electrolytic copper can be obtained. The content can be reduced and the silver content can be further reduced. Specifically, for example, by adding an impurity reducing agent composed of a nonionic surfactant having a hydrophobic group of polyethylene glycol or an aromatic ring and a hydrophilic group of a polyoxyalkylene group to the electrolytic solution, The surface becomes smooth, and silver ions and sulfate ions in the electrolytic solution hardly adhere to the electrolytic copper surface, so that the silver concentration and sulfur concentration of electrolytic copper can be significantly reduced.
不純物低減剤は、ポリエチレングリコール、または芳香族環の疎水基とポリオキシアルキレン基の親水基とを有する非イオン性界面活性剤からなる。芳香族環の疎水基とポリオキシアルキレン基の親水基とを有する非イオン性界面活性剤は、例えば、疎水基はフェニル基またはナフチル基などであり、モノフェニル、ナフチル、クミル、アルキルフェニル、スチレン化フェニルモノフェニル、ナフチル、クミル、アルキルフェニル、スチレン化フェニル、ジスチレン化フェニル、トリスチレン化フェニル、トリベンジルフェニルなどなどが挙げられる。親水基のポリオキシアルキレン基は、例えば、ポリオキシエチレン基、ポリオキシプロピレン基などであり、ポリオキシエチレン基とポリオキシプロピレン基の両方を含むものでも良い。また、親水基のポリオキシアルキレン基の付加モル数は２〜２０が好ましい。該付加モル数が２を下回ると不純物低減剤は電解液に溶解しない。また、該付加モル数が２０を上回ると電気銅の収率が低下する傾向がある。親水基のポリオキシアルキレン基の付加モル数は２〜１５であることがより好ましい。 The impurity reducing agent is composed of polyethylene glycol or a nonionic surfactant having a hydrophobic group of an aromatic ring and a hydrophilic group of a polyoxyalkylene group. The nonionic surfactant having a hydrophobic group of an aromatic ring and a hydrophilic group of a polyoxyalkylene group, for example, the hydrophobic group is a phenyl group or a naphthyl group, monophenyl, naphthyl, cumyl, alkylphenyl, styrene. Phenyl monophenyl, naphthyl, cumyl, alkylphenyl, styrenated phenyl, distyrenated phenyl, tristyrenated phenyl, tribenzylphenyl and the like. The hydrophilic polyoxyalkylene group is, for example, a polyoxyethylene group, a polyoxypropylene group, or the like, and may contain both a polyoxyethylene group and a polyoxypropylene group. Further, the number of moles of the polyoxyalkylene group of the hydrophilic group added is preferably 2 to 20. When the number of added moles is less than 2, the impurity reducing agent is not dissolved in the electrolytic solution. If the number of added moles exceeds 20, the yield of electrolytic copper tends to decrease. The number of moles of the polyoxyalkylene group added to the hydrophilic group is more preferably 2 to 15.
不純物低減剤の具体的な化合物は、例えば、ポリエチレングリコール、ポリオキシエチレンモノフェニルエーテル、ポリオキシエチレンメチルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンナフチルエーテル、ポリオキシエチレンスチレン化フェニルエーテル、ポリオキシエチレンジスチレン化フェニルエーテル、ポリオキシエチレントリスチレン化フェニルエーテル、ポリオキシエチレンクミルフェニルエーテル、ポリオキシプロピレンモノフェニルエーテル、ポリオキシプロピレンメチルフェニルエーテル、ポリオキシプロピレンオクチルフェニルエーテル、ポリオキシプロピレンドデシルフェニルエーテル、ポリオキシプロピレンナフチルエーテル、ポリオキシプロピレンスチレン化フェニルエーテル、ポリオキシプロピレンジスチレン化フェニルエーテル、ポリオキシプロピレントリスチレン化フェニルエーテル、ポリオキシプロピレンクミルフェニルエーテルなどである。 Specific compounds of the impurity reducing agent include, for example, polyethylene glycol, polyoxyethylene monophenyl ether, polyoxyethylene methyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene naphthyl ether, and polyoxyethylene naphthyl ether. Oxyethylene styrenated phenyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tristyrenated phenyl ether, polyoxyethylene cumyl phenyl ether, polyoxypropylene monophenyl ether, polyoxypropylene methyl phenyl ether, polyoxypropylene Octyl phenyl ether, polyoxypropylene dodecyl phenyl ether, polyoxypropylene naphthyl ether, polyoxypropylene styrenated phenyl ether, polyoxypropylene distyrenated phenyl ether, polyoxypropylene tristyrenated phenyl ether, polyoxypropylene cumyl phenyl ether And so on.
不純物低減剤の添加濃度（電解液中の濃度）は２〜５００mg/Lの範囲が好ましく、１０〜３００mg/Lの範囲がより好ましい。不純物低減剤の濃度が２mg/Lを下回り、また５００mg/Lより多くても電気銅の硫黄含有量を低減する効果は不十分である。 The added concentration of the impurity reducing agent (concentration in the electrolytic solution) is preferably in the range of 2 to 500 mg/L, more preferably in the range of 10 to 300 mg/L. If the concentration of the impurity reducing agent is less than 2 mg/L, and if it is more than 500 mg/L, the effect of reducing the sulfur content of electrolytic copper is insufficient.
本発明の添加剤は、電気銅の銀および塩素を低減するテトラゾール類と共に、電気銅の応力を緩和する平均重合度２００〜７００のポリビニルアルコールまたはその誘導体（応力緩和剤）を含むことによって、カソードに析出する電気銅の反りが殆どなく、かつ硫黄含有量がより少ない電気銅を得ることができる。
The additive of the present invention contains a polyvinyl alcohol having an average degree of polymerization of 200 to 700 or a derivative thereof (stress relaxation agent) that relaxes the stress of electrolytic copper together with tetrazoles that reduce silver and chlorine of electrolytic copper, thereby providing a cathode. It is possible to obtain electrolytic copper that has almost no warpage of electrolytic copper that is deposited on the steel and has a lower sulfur content.
上記応力緩和剤は、カソードに析出する電気銅の電着応力を緩和して該電気銅がカソードから落下するのを防止する。また、電着応力が緩和されることによって電気銅がカソードに長時間安定に保持されるので、緻密に析出した表面が平滑な電気銅が得られる。 The stress relaxation agent relaxes the electrodeposition stress of the electrolytic copper deposited on the cathode and prevents the electrolytic copper from falling from the cathode. In addition, since the electrolytic copper is held on the cathode stably for a long time by relaxing the electrodeposition stress, electrolytic copper having a finely deposited surface and smooth surface can be obtained.
応力緩和剤として用いるポリビニルアルコール誘導体は、例えば、カルボキシ変性ポリビニルアルコール、エチレン変性ポリビニルアルコール、またはポリオキシエチレン変性ポリビニルアルコールである。 The polyvinyl alcohol derivative used as the stress relaxation agent is, for example, carboxy-modified polyvinyl alcohol, ethylene-modified polyvinyl alcohol, or polyoxyethylene-modified polyvinyl alcohol.
上記ポリビニルアルコールまたはその誘導体はケン化率７０〜９９mol％が好ましく、ポリビニルアルコールまたはその誘導体のケン化率を７０〜９０mol％とすることがより好ましい。ケン化率が７０mol％未満であると、電着応力を緩和する効果が乏しくなる。一方、完全にケン化したもの（ケン化率１００mol％）は溶解性が著しく低下し、ポリビニルアルコールまたはその誘導体を電解液に溶かし込めなくなる。 The saponification rate of the polyvinyl alcohol or its derivative is preferably 70 to 99 mol %, and more preferably the saponification rate of the polyvinyl alcohol or its derivative is 70 to 90 mol %. If the saponification rate is less than 70 mol %, the effect of relaxing the electrodeposition stress becomes poor. On the other hand, a completely saponified product (saponification rate: 100 mol %) has a markedly reduced solubility, and polyvinyl alcohol or its derivative cannot be dissolved in the electrolytic solution.
上記応力緩和剤のポリビニルアルコールまたはその誘導体は平均重合度２００〜７００が好ましい。ポリビニルアルコールおよびその誘導体の基本構造は水酸基の完全ケン化型と酢酸基を有する部分ケン化型から成り立っており、ポリビニルアルコールおよびその誘導体の重合度はその両者の総数であり、平均重合度は重合度の平均値である。平均重合度はJISK6726のポリビニルアルコール試験方法に基づいて測定することができる。
The average degree of polymerization of polyvinyl alcohol or its derivative as the stress relaxation agent is preferably 200 to 700 . The basic structure of polyvinyl alcohol and its derivatives consists of the completely saponified type of hydroxyl groups and the partially saponified type having an acetic acid group.The degree of polymerization of polyvinyl alcohol and its derivatives is the total number of both, and the average degree of polymerization is It is the average of degrees. The average degree of polymerization can be measured based on the polyvinyl alcohol test method of JIS K6726.
ポリビニルアルコールまたはその誘導体の平均重合度が２００未満であると、電着応力を緩和する効果が乏しくなる。また、ポリビニルアルコールまたはその誘導体の平均重合度が２００未満のものは、製造上困難なものもあり、かつ一般的に使用されていないため入手が難しい。一方、上記平均重合度が７００を大幅に超えると、電着応力を緩和する効果が乏しくなるのでカソードに析出した電気銅に反りが発生するようになり、さらに電着抑制効果が生じて電気銅の収率が低下する傾向がある。従って、ポリビニルアルコールまたはその誘導体の平均重合度は２００〜７００が好ましい。
If the average degree of polymerization of polyvinyl alcohol or its derivative is less than 200, the effect of relaxing the electrodeposition stress becomes poor. In addition, polyvinyl alcohol or a derivative thereof having an average degree of polymerization of less than 200 is difficult to obtain in some cases because it is difficult to manufacture and is not generally used. On the other hand, when the average degree of polymerization is significantly higher than 700, the effect of relaxing the electrodeposition stress becomes poor, so that the electric copper deposited on the cathode is warped , and the effect of suppressing the electrodeposition is further produced. Yield tends to decrease. Therefore, the average degree of polymerization of polyvinyl alcohol or its derivative is preferably 200 to 700 .
上記応力緩和剤の添加濃度（電解液中の濃度）は０.１〜１００mg/Lの範囲が好ましく、１〜５０mg/Lの範囲がより好ましい。応力緩和剤の添加濃度が０.１mg/Lより少ないと電気銅の反りを抑制する効果が不十分であり、また１００mg/Lより多いと、電気銅の反りを抑制する効果が見られず、粗大なデンドライトが発生する。 The added concentration (concentration in the electrolytic solution) of the stress relaxation agent is preferably in the range of 0.1 to 100 mg/L, more preferably in the range of 1 to 50 mg/L. If the added concentration of the stress relaxation agent is less than 0.1 mg/L, the effect of suppressing the warp of electrolytic copper is insufficient, and if it is more than 100 mg/L, the effect of suppressing the warp of electrolytic copper is not seen, Coarse dendrites are generated.
本発明の銀塩素低減剤は、硫酸銅水溶液、硝酸銅水溶液、またはピロリン酸銅水溶液の何れの銅電解液についても使用することができる。本発明の銀塩素低減剤と共に上記不純物低減剤または応力緩和剤、あるいはこれらの両方を用いる場合にも上記何れの電解液について使用することができる。銅電解は一般の銅電解条件下で行うことができる。通常、電解液の銅濃度は５〜９０g/Lが好ましく、２０〜７０g/Lがより好ましい。 The silver chlorine reducing agent of the present invention can be used in any copper electrolytic solution of a copper sulfate aqueous solution, a copper nitrate aqueous solution, or a copper pyrophosphate aqueous solution. When the above-mentioned impurity reducing agent or stress relieving agent or both of them are used together with the silver chlorine reducing agent of the present invention, it can be used for any of the above electrolytic solutions. Copper electrolysis can be performed under general copper electrolysis conditions. Usually, the copper concentration of the electrolytic solution is preferably 5 to 90 g/L, more preferably 20 to 70 g/L.
なお、本発明の銀塩素低減剤、あるいは該銀塩素低減剤と共に不純物低減剤や応力緩和を使用する場合、塩化銅浴以外の電解液については、電解液の塩化物イオン濃度は２００mg/L以下が好ましい。塩化物イオン濃度が２００mg/Lを上回ると、銀塩素低減剤の塩素低減効果が低下して電気銅に塩化物が取り込まれやすくなり、電気銅の純度が低下するので好ましくない。なお、塩化物イオン濃度の下限値を５mg/Lとすることが好ましく、塩化物イオン濃度を５〜１５０mg/Lとすることがより好ましい When using the silver chlorine reducing agent of the present invention, or an impurity reducing agent or stress relaxation together with the silver chlorine reducing agent, the chloride ion concentration of the electrolytic solution is 200 mg/L or less for electrolytic solutions other than the copper chloride bath. Is preferred. If the chloride ion concentration exceeds 200 mg/L, the chlorine-reducing effect of the silver chlorine-reducing agent is reduced, chloride is easily incorporated into electrolytic copper, and the purity of electrolytic copper is reduced, which is not preferable. The lower limit of the chloride ion concentration is preferably 5 mg/L, more preferably the chloride ion concentration is 5 to 150 mg/L.
本実施形態の添加剤が上記銀塩素低減剤と上記不純物低減剤とを含む場合、該添加剤を電解液（銅電解液）に添加したときの電解液中における濃度比が（１：０.２〜２０００）（銀塩素低減剤濃度：不純物低減剤濃度）となるように上記銀塩素低減剤と上記不純物低減剤とが混合されていることが好ましい。また、本実施形態の添加剤が上記不純物低減剤と上記応力緩和剤とを含む場合、該添加剤を電解液（銅電解液）に添加したときの電解液中における濃度比が（１：０.０１〜１）（不純物低減剤濃度：応力緩和剤濃度）となるように上記不純物低減剤と上記応力緩和剤とが混合されていることが好ましい。 When the additive of the present embodiment contains the silver chlorine reducing agent and the impurity reducing agent, the concentration ratio in the electrolytic solution when the additive is added to the electrolytic solution (copper electrolytic solution) is (1:0. 2-2000) (silver chlorine reducing agent concentration: impurity reducing agent concentration) is preferably mixed with the silver chlorine reducing agent and the impurity reducing agent. Further, when the additive of the present embodiment contains the impurity reducing agent and the stress relaxing agent, the concentration ratio in the electrolytic solution when the additive is added to the electrolytic solution (copper electrolytic solution) is (1:0). 0.01-1) (impurity reducing agent concentration: stress relaxation agent concentration) is preferably mixed with the impurity reducing agent and the stress relaxation agent.
銅電解精錬において、本発明の銀塩素低減剤を用いることによって、銀含有量および塩素含有量ない高純度の電気銅を得ることができる。具体的には、塩素含有量５０質量ppm以下および銀含有量１質量ppm以下の高純度電気銅を得ることができる。 By using the silver chlorine reducing agent of the present invention in copper electrolytic refining, high-purity electrolytic copper having no silver content and no chlorine content can be obtained. Specifically, high-purity electrolytic copper having a chlorine content of 50 mass ppm or less and a silver content of 1 mass ppm or less can be obtained.
銅電解精錬において、本発明の銀塩素低減剤と共に不純物低減剤や応力緩和剤を用いることによって、さらに銀含有量が少なく、また硫黄含有量が少なく、カソードからの反りや剥離の無い高純度の電気銅を得ることができる。 In the copper electrolytic refining, by using the impurity reducing agent and the stress relieving agent together with the silver chlorine reducing agent of the present invention, the silver content is further reduced, the sulfur content is also low, and there is no warp or peeling from the cathode. It is possible to obtain electrolytic copper.
以下に本発明の実施例を比較例と共に示す。
実施例および比較例において、(イ)電気銅の硫黄濃度、塩素濃度および銀濃度はＧＤ−ＭＳ（グロー放電質量分析法）によって電気銅の中央部を測定した。(ロ)電気銅表面の光沢度は、JIS Z 8741:1997(ISO 2813:1994、ISO 7668:1986に対応)に基づき、光沢度計（日本電色社製品、HANDY GLOSSMETER PG-1M）を用いて入射角６０°の条件で電気銅の中央部を測定した。光沢度が低いと電気銅表面に付着した電解液を十分に水洗洗浄し難いために電気銅表面に電解液が残留し易くなり、電気銅の純度が低下する。また電気銅に粗大なデンドライトが発生したものは、光沢度計が電気銅の上に置けず、光沢度が測定できないため、×とした。(ハ)電気銅の反りを目視観察によって判断した。反りが見られないものを○印、反りが小さいものを△、反りが大きく剥離が見られるものを×印で示した。（ニ）電気銅に粗大なデンドライトが見られるものをあり、見られないものをなしとした。
Hereinafter, examples of the present invention will be shown together with comparative examples.
In the examples and comparative examples, (a) the sulfur concentration, chlorine concentration and silver concentration of electrolytic copper were measured in the central portion of electrolytic copper by GD-MS (glow discharge mass spectrometry). (B) The glossiness of electrolytic copper surface is based on JIS Z 8741:1997 (corresponding to ISO 2813:1994, ISO 7668:1986) using a gloss meter (product of Nippon Denshoku Co., Ltd., HANDY GLOSSMETER PG-1M). The central part of the electrolytic copper was measured under the condition of an incident angle of 60°. When the glossiness is low, it is difficult to sufficiently wash and wash the electrolytic solution adhering to the surface of the electrolytic copper, so that the electrolytic solution tends to remain on the surface of the electrolytic copper, and the purity of the electrolytic copper decreases. In addition, for those in which coarse dendrites were generated on the electrolytic copper, the gloss meter could not be placed on the electrolytic copper, and the glossiness could not be measured. (C) The warp of electrolytic copper was judged by visual observation. The one with no warp is indicated by a circle, the one with a small warp is indicated by a triangle, and the one with a large warp and peeling is indicated by a cross. (D) Some electrolytic copper showed coarse dendrites, and none was observed.
〔試験例１〕
本発明の添加剤に含まれる銀塩素低減剤（Ａ、Ｂ、Ｃ）について、酸濃度５０g/L、銅濃度５０g/L、塩化物イオン濃度１００mg/Lに調整した硫酸銅水溶液、硝酸銅水溶液、またはピロリン酸銅水溶液を銅電解液として用い、該銅電解液に、上記銀塩素低減剤を表１に示す濃度になるように加えた。また、アノードには硫黄濃度５質量ppmおよび銀濃度８質量ppmの電気銅を用い、カソードにはＳＵＳ３１６の板を用いた。電流密度を２００A/m２、浴温３０℃にて５日間銅電解を行ない、１２時間ごとにＯＤＳカラムを用いたＨＰＬＣによって銀塩素低減剤濃度を測定し、銀塩素低減剤濃度が初期の濃度を維持するように減少分を補給して電気銅をＳＵＳ板上に電析させた。使用した銀塩素低減剤（Ａ、Ｂ、Ｃ）を以下に示す。結果を表１に示す。
銀塩素低減剤Ａ：１Ｈ−テトラゾール
銀塩素低減剤Ｂ：５−アミノ−１Ｈ−テトラゾール
銀塩素低減剤Ｃ：５−メチル−１Ｈ−テトラゾール
[Test Example 1]
Regarding the silver chlorine reducing agents (A, B, C) contained in the additive of the present invention, an aqueous solution of copper sulfate and an aqueous solution of copper nitrate adjusted to have an acid concentration of 50 g/L, a copper concentration of 50 g/L and a chloride ion concentration of 100 mg/L. Alternatively, an aqueous solution of copper pyrophosphate was used as a copper electrolytic solution, and the silver chloride reducing agent was added to the copper electrolytic solution so that the concentration was as shown in Table 1. Further, electrolytic copper having a sulfur concentration of 5 mass ppm and a silver concentration of 8 mass ppm was used for the anode, and a SUS316 plate was used for the cathode. Copper electrolysis was carried out at a current density of 200 A/m 2 and a bath temperature of 30° C. for 5 days, and the silver chlorine reducing agent concentration was measured by HPLC using an ODS column every 12 hours. The silver chlorine reducing agent concentration was the initial concentration. The electrolytic copper was electrodeposited on the SUS plate by replenishing the reduced amount so as to maintain The silver chlorine reducing agents (A, B, C) used are shown below. The results are shown in Table 1.
Silver chlorine reducing agent A: 1H-tetrazole Silver chlorine reducing agent B: 5-Amino-1H-tetrazole Silver chlorine reducing agent C: 5-Methyl-1H-tetrazole
表１に示すように、本発明の銀塩素低減剤を添加して製造した電気銅は、何れも反りが小さく、硫黄濃度１０質量ppm未満、銀濃度２質量ppm未満、および塩素濃度８０質量ppm未満の不純物の少ない高純度の電気銅が得られる。特に、銀塩素低減剤Ａを用い、該Ａの濃度を０.１〜３０mg/Lの範囲に調整して製造した電気銅は、硫黄濃度７.３質量ppm以下、銀濃度１質量ppm以下、および塩素濃度５１質量ppm以下であり、硫黄、銀、および塩素の各濃度が大幅に低減され、かつ電気銅表面に粗大なデンドライトが無く、光沢度０.８以上の高品位の電気銅を得ることができる。 As shown in Table 1, all the electrolytic copper produced by adding the silver chlorine reducing agent of the present invention has a small warp, a sulfur concentration of less than 10 mass ppm, a silver concentration of less than 2 mass ppm, and a chlorine concentration of 80 mass ppm. High-purity electrolytic copper with less impurities than is obtained. In particular, electrolytic copper produced by using the silver chlorine reducing agent A and adjusting the concentration of the A in the range of 0.1 to 30 mg/L has a sulfur concentration of 7.3 mass ppm or less, a silver concentration of 1 mass ppm or less, And chlorine concentration is 51 mass ppm or less, each concentration of sulfur, silver, and chlorine is significantly reduced, and there is no coarse dendrite on the surface of electrolytic copper, and high-quality electrolytic copper with a glossiness of 0.8 or more is obtained. be able to.
また、銀塩素低減剤Ｂを用い、該Ｂの濃度１０mg/Lにて製造した電気銅は、硫酸浴および硝酸浴の何れでも、硫黄濃度５.８質量ppm以下、銀濃度０.５２質量ppm以下、塩素濃度４２質量ppm以下であって光沢度０.９以上の粗大なデンドライトの無い高品位電気銅である。さらに、銀塩素低減剤Ｃを用い、該Ｃの濃度１０mg/Lにて製造した電気銅は、硫酸浴およびピロリン酸浴の何れでも、硫黄濃度６.２質量ppm以下、銀濃度０.６８質量ppm以下、塩素濃度４６質量ppm以下の粗大なデンドライトの無い高品位電気銅であり、ピロリン酸浴を用いた電気銅は光沢度が０.５であるが、硫酸浴を用いた電気銅は光沢度が０.７であって光沢度の高い電気銅を得ることができる。 Further, the electrolytic copper produced using the silver chlorine reducing agent B at a concentration of the B of 10 mg/L has a sulfur concentration of 5.8 mass ppm or less and a silver concentration of 0.52 mass ppm both in the sulfuric acid bath and the nitric acid bath. Hereafter, it is a high-grade electrolytic copper having a chlorine concentration of 42 mass ppm or less and a glossiness of 0.9 or more without coarse dendrites. Furthermore, the electrolytic copper produced using the silver chlorine reducing agent C at a concentration of 10 mg/L of C has a sulfur concentration of 6.2 mass ppm or less and a silver concentration of 0.68 mass in both a sulfuric acid bath and a pyrophosphoric acid bath. It is a high-grade electrolytic copper that does not have coarse dendrites with ppm or less and a chlorine concentration of 46 mass ppm or less. The electrolytic copper using a pyrophosphoric acid bath has a gloss level of 0.5, while the electrolytic copper using a sulfuric acid bath is bright. It is possible to obtain electrolytic copper with a degree of 0.7 and high gloss.
〔実施例１〕
表２に示すように、試験例１の銀塩素低減剤（Ａ、Ｂ、Ｃ）および他の銀塩素低減剤Ｄ（５−フェニル−１Ｈ−テトラゾール）と共に、応力緩和剤（Ｌ、Ｍ、Ｎ、Ｏ）を含む本発明の添加剤を用いた。また、不純物低減剤（Ｆ、Ｇ、Ｈ、Ｉ、Ｊ、Ｋ）を含む添加剤を用いた。これらの添加剤について、銀塩素低減剤の添加濃度を１０mg/L、不純物低減剤の添加濃度を１０、１００mg/Lにし、応力添加剤の濃度を１０mg/Lとした。銅電解液中の酸濃度、銅濃度、塩化物濃度およびその他の電解条件は試験例１と同様の条件で銅電解精錬を行い、電気銅を製造した。使用した不純物低減剤（Ｆ〜Ｋ）および応力緩和剤（Ｌ〜Ｏ）を以下に示す。
不純物低減剤Ｆ：平均分子量１５００のポリエチレングリコール。
不純物低減剤Ｇ：平均分子量２５００のポリエチレングリコール。
不純物低減剤Ｈ：エチレンオキサイドの付加モル数が５のポリオキシエチレンモノフェニルエーテル。
不純物低減剤Ｉ：エチレンオキサイドの付加モル数が１０のポリオキシエチレンモノフェニルエーテル。
不純物低減剤Ｊ：エチレンオキサイドの付加モル数が７のポリオキシエチレンナフチルエーテル。
不純物低減剤Ｋ：エチレンオキサイドの付加モル数が１５のポリオキシエチレンナフチルエーテル。
応力緩和剤Ｌ：ケン化率が８８mol％で平均重合度が３００のポリビニルアルコール。
応力緩和剤Ｍ：ケン化率が８８mol％で平均重合度が６００のポリビニルアルコール。
応力緩和剤Ｎ：ケン化率が９８mol％で平均重合度が６００のカルボキシ変性ポリビニルアルコール。
応力緩和剤Ｏ：ケン化率が９８ｍｏｌ％で平均重合度が７００のポリオキシエチレン変性ポリビニルアルコール。
結果を表２に示す。なお、表２の試料No.21、No.23〜26、No.28、No.30、No.32、No.34〜36、No.38、No.40、No.42、No.44、No.46、No.48、No.50、No.52が本発明の添加剤を使用した結果であり、その他は参考例である。
[Example 1]
As shown in Table 2, together with the silver chlorine reducing agent (A, B, C) of Test Example 1 and another silver chlorine reducing agent D (5-phenyl-1H-tetrazole), a stress relaxation agent (L, M, N) was used. , O) were used. An additive containing an impurity reducing agent (F, G, H, I, J, K) was used. Regarding these additives, the concentration of silver chloride reducing agent added was 10 mg/L, the concentration of impurity reducing agent added was 10, 100 mg/L, and the concentration of stress additive was 10 mg/L. Copper electrolytic refining was performed under the same conditions as in Test Example 1 for the acid concentration, copper concentration, chloride concentration and other electrolysis conditions in the copper electrolytic solution to produce electrolytic copper. The impurity reducing agents (F to K) and stress relaxation agents (L to O) used are shown below.
Impurity reducing agent F: polyethylene glycol having an average molecular weight of 1500.
Impurity reducing agent G: Polyethylene glycol having an average molecular weight of 2500.
Impurity reducing agent H: Polyoxyethylene monophenyl ether in which the addition mole number of ethylene oxide is 5.
Impurity reducing agent I: Polyoxyethylene monophenyl ether in which the added mole number of ethylene oxide is 10.
Impurity reducing agent J: Polyoxyethylene naphthyl ether in which the added mole number of ethylene oxide is 7.
Impurity reducing agent K: Polyoxyethylene naphthyl ether in which the added mole number of ethylene oxide is 15.
Stress relaxation agent L: polyvinyl alcohol having a saponification rate of 88 mol% and an average degree of polymerization of 300.
Stress relaxation agent M: Polyvinyl alcohol having a saponification rate of 88 mol% and an average degree of polymerization of 600.
Stress relaxation agent N: carboxy-modified polyvinyl alcohol having a saponification rate of 98 mol% and an average degree of polymerization of 600.
Stress relaxation agent O: Polyoxyethylene-modified polyvinyl alcohol having a saponification rate of 98 mol% and an average degree of polymerization of 700.
The results are shown in Table 2. The samples No. 21, No. 23 to 26, No. 28, No. 30, No. 32, No. 34 to 36, No. 38, No. 40, No. 42, No. 44, No. 46, No. 48, No. 50 and No. 52 are the results of using the additive of the present invention, and the others are reference examples.
表２に示すように、本発明の銀塩素低減剤と不純物低減剤を用いて製造した電気銅は、硫黄濃度１.２１ppm以下、銀濃度０.５ppm以下、塩素濃度３０ppm以下の高純度電気銅であって、光沢度２以上の反りの少ない高品位電気銅である。さらに、応力緩和剤を併用したものは、反りの無い高品位電気銅を得ることができる。
また、表２に示す電気銅は、本発明の銀塩素低減剤と共に不純物低減剤を併用することによって、電気銅の硫黄濃度、銀濃度、および塩素濃度が大幅に低減されており、また光沢度の高い電気銅を得ることができる。
As shown in Table 2, electrolytic copper produced by using the silver chlorine reducing agent and the impurity reducing agent of the present invention is high-purity electrolytic copper having a sulfur concentration of 1.21 ppm or less, a silver concentration of 0.5 ppm or less, and a chlorine concentration of 30 ppm or less. In addition, it is a high-grade electrolytic copper with a degree of gloss of 2 or more and less warpage. Further, the one using the stress relaxation agent together can obtain high-grade electrolytic copper free from warpage.
Further, in the electrolytic copper shown in Table 2, the sulfur concentration, silver concentration, and chlorine concentration of the electrolytic copper were significantly reduced by using the silver chlorine reducing agent of the present invention together with the impurity reducing agent, and the glossiness was improved. High electrolytic copper can be obtained.
〔比較例１〕
本発明の銀塩素低減剤を用いずに、不純物低減剤Ｆを用い、あるいは不純物低減剤Ｆと共に応力緩和剤Ｉを用い、その他は実施例１と同様の条件で銅電解精錬を行い、電気銅を製造した。不純物添加剤Ｆおよび応力緩和剤Ｍの添加濃度は何れも１０mg/Lである。この結果を表３に示した。表３に示すように、本例の試料（No.30〜No.32）は何れも電気銅の塩素量が格段に多く、実施例１の塩素量の約２倍〜約６倍であり、銀含有量も実施例１の銀含有量の約１.１倍〜約５倍であった。
[Comparative Example 1]
Without using the silver chlorine reducing agent of the present invention, the impurity reducing agent F was used, or the stress reducing agent I was used together with the impurity reducing agent F, and otherwise electrolytic copper refining was performed under the same conditions as in Example 1 to obtain electrolytic copper. Was manufactured. The addition concentrations of the impurity additive F and the stress relaxation agent M are both 10 mg/L. The results are shown in Table 3. As shown in Table 3, in each of the samples (No. 30 to No. 32) of this example, the chlorine content of electrolytic copper was remarkably large, which was about 2 to 6 times the chlorine content of Example 1. The silver content was about 1.1 times to about 5 times the silver content of Example 1.
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